Nole produced another great display, recording a 6-0, 6-1 win over world no.62 Pablo Carreno Busta of Spain (LL) in just 47 minutes.
Djokovic needed just 45 minutes to advance into the third round at the Monte-Carlo Rolex Masters. He beat Albert Montanes 6-1, 6-0.
Defending champion Novak is seeded no.2 and has a first-round BYE. He will open his campaign against Albert Montanes.
The World Group play-offs will take place on 12-14 September.
After winning the first two Masters 1000 events in 2014, Novak comes back to Europe full of confidence ahead of the clay season.
Nole, who completed the Indian Wells-Miami double on Sunday, has closed the gap on Rafael Nadal at the top of the latest ATP rankings.
Novak clinched his 18th ATP World Tour Masters 1000 title on Sunday with a 6-3, 6-3 victory over top seed Rafael Nadal.
Second seed in Key Biscayne moved on to the finals on Friday after his semi-final opponent Kei Nishikori (JPN, 20) withdrew from the tournament with a left groin injury.
Novak advanced into the Miami Masters last four with a 7-5, 6-3 win over no.6 seed and defending champion Andy Murray on Wednesday.
Nole defeated Spaniard Tommy Robredo 6-3, 7-5 in 1 hour and 22 minutes to advance into the Sony Open Tennis last 8.
04.05. - 11.05.2014.